JP7382732B2 - putty composition - Google Patents

Description

The present invention relates to a putty composition, a putty molded body, and a method for producing a putty molded body.

BACKGROUND ART Conventionally, in order to install equipment, parts, etc., a process of pouring a resin filler into a predetermined space and then curing it has been performed. In this case, in order to prevent the poured filler from leaking out and making it impossible to fill the specified space, an enclosure (dam) is installed to prevent the filler from leaking out, and a dam is installed to prevent the filler from leaking out. A sealing material (dam reinforcing material) is installed to prevent leakage, and then the filler is poured.

An example of this is when a marine filler is applied around a stern tube of a vessel. Specific examples in this case include the embodiments shown in FIGS. 4 and 5 of Patent Document 1. In these figures, the sealing sponges shown as 33 and 35 correspond to the dam, and the sealing resins shown as 34 and 36 correspond to the sealing material.
Further, the above-mentioned sealing material is also used when applying a marine filler to various marine equipment such as around the rudder head bearing.

A putty composition is used as the sealing material.
The putty composition is also used for filling and repairing defective parts of structures.

As the putty composition, a putty-like two-component epoxy resin composition containing whiskers and fibrillated fibers is known (Patent Document 2).

Japanese Patent Application Publication No. 2002-160697 JP2006-219624A

Since the putty composition has a high viscosity, it is applied using a spatula or a trowel. It is required that the putty composition has excellent separability from the putty composition (when removing the spatula or trowel from the putty composition, the composition does not stick to the spatula or trowel, and it is difficult to cause stringiness). Hereinafter, this separability will also be referred to as "sharpness."

In addition, depending on the application, such as applying marine filler to rudder head bearings, it is necessary to apply the putty composition to the area where the applied putty composition surface faces directly downward (in the direction of gravity). In such cases, the composition is particularly required to not sag and to have excellent shape retention. Hereinafter, this shape retention is also referred to as "sagging resistance".

Furthermore, when filling the filler, the filler may be pumped and filled using a pump or the like. In this case, since pressure is also applied to the sealing material, the molded body formed from the putty composition (putty molded body) is also required to have appropriate flexibility to withstand such pressure.

However, conventional putty compositions have room for improvement in terms of the sharpness and sagging resistance, as well as the flexibility of the resulting putty molded product.

The present invention has been made in view of these circumstances, and an object of the present invention is to provide a putty composition that can form a putty molded body having appropriate flexibility and has excellent sharpness and sag resistance.

The inventors of the present invention have conducted extensive studies on methods for solving the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by using a predetermined composition, and have completed the present invention. A configuration example of the present invention is as follows.

[1] A putty composition containing an epoxy compound (A), an aliphatic amine (B) and a silica (C),
The content of the silica (C) is 5% by mass or more based on 100% by mass of nonvolatile content of the putty composition.
Putty composition.

[2] The putty composition according to [1], wherein the silica (C) is hydrophilic fumed silica.

[3] The putty composition according to [1] or [2], further containing an acrylonitrile butadiene copolymer (D).
[4] The putty composition according to [3], wherein the content of the copolymer (D) is 10 to 40% by mass based on 100% by mass of nonvolatile content of the putty composition.

[5] The putty composition according to any one of [1] to [4], wherein the epoxy compound (A) contains a fatty acid-modified epoxy compound (A1).

[6] The putty composition according to any one of [1] to [5], which is for ships.

[7] A putty molded body formed from the putty composition according to any one of [1] to [6].
[8] A method for producing a putty molded body, comprising the step of applying the putty composition according to any one of [1] to [6] to a construction site and then curing the putty composition to produce a putty molded body.

According to the present invention, it is possible to obtain a putty composition that has excellent sharpness and excellent shape-retention properties that do not sag even when applied thickly to vertical surfaces or directly above (ceiling surfaces), etc., and that has appropriate flexibility when molded into putty. Can form a body.
Further, according to the present invention, even in the case of a two-component putty composition consisting of a base component and a curing agent component, it is possible to obtain a putty composition that has excellent miscibility between the base component and the curing agent component. can.

FIG. 1 is a photograph showing an example of a case where the coating property (cutting property) of the example is ◯. FIG. 2 is a photograph showing an example of the case where the coating property (cutting property) of the example is rated as x.

≪Putty composition≫
The putty composition according to the present invention (hereinafter also referred to as "the present composition") contains an epoxy compound (A) (hereinafter also referred to as "component (A)". The same applies to other components), an aliphatic amine (B ) and silica (C), and the content of the silica (C) is 5% by mass or more based on 100% by mass of the nonvolatile content of the present composition.
Since the present composition contains a specific component (B) and a specific amount of component (C), it can be made into a putty composition and exhibits the above-mentioned effects.

Incidentally, the nonvolatile content of the present composition means the heating residue obtained according to JIS K 5601-1-2:2008 (heating temperature: 125°C, heating time: 60 minutes).

The putty composition refers to a clay-like composition that does not substantially exhibit fluidity unless external force is applied to it. Preferably, the composition has a viscosity of 150 Pa·s/25°C or more as measured with an E-type viscometer.

Although the present composition may be a one-component type composition, it is usually a two-component type composition consisting of a main component containing component (A) and a curing agent component containing component (B). It is. Moreover, if necessary, a three-component or more composition may be used.
When the present composition is a two-component or more composition, the component (C) may be included in the main component, the curing agent component, or the third component. It may be contained in two or more of these components.
These main agent components and curing agent components (and third components, etc.) are usually stored, stored, transported, etc. in separate containers, and mixed immediately before use.

This composition may contain volatile components such as solvents as long as it has a viscosity within the above range, but it can easily yield a composition with excellent sag resistance and form a putty molded body. From the viewpoint of suppressing curing shrinkage during drying, it is preferable that volatile components are not substantially contained.
"Substantially free" means that the content of volatile components in the composition is preferably 1% by mass or less, more preferably 0.5% by mass or less.

The specific gravity of the present composition is preferably 0.9 to 1.5, more preferably 1.0 to 1.3, from the viewpoint of easily obtaining a composition with better sag resistance.
In the present invention, the specific gravity of the composition is a value measured based on JIS Z 8807:2012.

Since the present composition exhibits the above-mentioned effects, it is suitably used as a sealing material when pouring a resin filler into a predetermined space for installing or fixing equipment or parts, etc., and is particularly suitable for use in ships. Specifically, it is particularly suitable for use in ship stern tubes and rudder head bearings.
The composition can also be used for filling and repairing defective parts of structures.

<Epoxy compound (A)>
Component (A) is a compound other than component (D) below and is not particularly limited as long as it has an epoxy group, including fatty acid-modified epoxy compound (A1) and monoepoxy compounds other than the compound (A1). (A2), and epoxy compounds (A3) other than the compounds (A1) and (A2).
The present composition preferably contains component (A1) from the viewpoint of easily obtaining a composition having excellent stretchability, flexibility, and sharpness, and a putty molded product. (A2) or (A3), and particularly preferably components (A1) to (A3).
Component (A) may be used alone or in combination of two or more.

The content of component (A) based on 100% by mass of the non-volatile content of the present composition is such that it is possible to easily obtain a composition or a putty molded article that has appropriate flexibility and has excellent adhesion to the object to be coated. From these points of view, it is preferably 10 to 60% by mass, more preferably 20 to 45% by mass.

[Fatty acid modified epoxy compound (A1)]
Component (A1) can be obtained, for example, by reacting one or more epoxy compounds (a1) with one or more fatty acids or derivatives thereof (a2), and , can be obtained by introducing an epoxy group into a fatty acid or its derivative.
By using component (A1), it is possible to easily form a putty molded body having excellent elongation, elasticity, and sharpness, and having appropriate flexibility.
Component (A1) may be used alone or in combination of two or more.

Examples of the epoxy compound (a1) include bisphenol-type epoxy resins, glycidyl ester-type epoxy resins, glycidylamine-type epoxy resins, novolak-type epoxy resins, cresol-type epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, and epoxy resins. Epoxy resins such as oil-based epoxy resins, specifically epoxy resins exemplified below (A3), epichlorohydrin, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, 1,3-propanediol diglycidyl ether, 1 , 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether and the like.

The content of the structural unit derived from the epoxy compound (a1) in the component (A1) is preferably set to It is 15 to 75% by weight, more preferably 20 to 60% by weight.

The fatty acid or its derivative (a2) is preferably a higher fatty acid or its derivative from the viewpoint of imparting elasticity to the resulting composition or putty molded product.
The higher fatty acid refers to an aliphatic carboxylic acid having 8 or more carbon atoms, preferably an aliphatic carboxylic acid having 12 or more carbon atoms. Preferably, the derivative is triglyceride, which is an ester of higher fatty acid and glycerin.

The fatty acid is preferably an unsaturated fatty acid. The unsaturated fatty acid preferably has 12 to 24 carbon atoms, more preferably 16 to 18 carbon atoms, including the carbon atoms of the carboxyl group, and has one or two unsaturated bonds in one molecule. A carboxylic acid having at least 1 is preferable. Examples of such unsaturated fatty acids include fatty acids having one unsaturated bond such as oleic acid, elaidic acid, and ricinoleic acid; fatty acids having two unsaturated bonds such as linoleic acid; and fatty acids having two unsaturated bonds such as linolenic acid and arachidonic acid. Examples include fatty acids having three or more unsaturated bonds. Furthermore, fatty acids obtained from animals and plants can also be used, and examples of the fatty acids include castor oil fatty acids, soybean oil fatty acids, tall oil fatty acids, and linseed oil fatty acids. Furthermore, the fatty acid may be a dimer acid that is a dimer of unsaturated fatty acids.
Specific examples of the fatty acid derivatives include castor oil, soybean oil, tall oil, and linseed oil.

The inclusion of a structural unit derived from the fatty acid or its derivative (a2) in component (A1) makes it possible to easily obtain a composition and a putty molded article with excellent drying properties, pigment dispersibility, and corrosion resistance. The amount is preferably 15-85% by weight, more preferably 20-80% by weight.

When the epoxy compound (a1) and the fatty acid or its derivative (a2) are reacted, for example, dimethylbenzylamine, triethylamine, etc. are used to suppress side reactions such as etherification reaction. Good too. Further, a polymerization inhibitor such as a radical polymerization inhibitor may be used.

Furthermore, when the epoxy compound (a1) and the fatty acid or its derivative (a2) are reacted, a polyhydric alcohol may be used.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, and triethylene glycol. , cyclohexanedimethanol, hydrogenated bisphenol A, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol.

Examples of the method for introducing an epoxy group into the fatty acid or its derivative include a method of oxidizing the double bond of the fatty acid or its derivative to form an epoxy group. Component (A1) obtained by such a method includes, for example, a linseed oil-modified epoxy resin obtained by oxidizing the double bonds of linseed oil whose main component is triglyceride of linoleic acid.

As component (A1), a castor oil-modified epoxy resin is particularly preferred because it has excellent elongation, stretchability, and sharpness, and can easily form a putty molded body having appropriate flexibility.

As component (A1), a compound synthesized by a conventionally known method may be used, or a commercially available product may be used.
Examples of such commercial products include castor oil-modified epoxy resins such as ERISYS GE-35 (manufactured by CVC Thermoset Specialties) and HELOXY 505 (manufactured by Hexion), and dimer acid-modified epoxy resins such as ERISYS GS-120. (manufactured by CVC Thermoset Specialties), jER 871, jER 872 (manufactured by Mitsubishi Chemical Corporation), and the like.

The epoxy equivalent of component (A1) is preferably 50 to 1,000, more preferably It is 100-800.
The epoxy equivalent in the present invention is calculated based on JIS K 7236:2001.

When the present composition contains component (A1), it is possible to easily obtain a composition or a putty molded body having appropriate flexibility and excellent adhesion to the object to be coated. The content of component (A1) based on 100% by mass of the nonvolatile content of the composition is preferably 3 to 30% by mass, more preferably 5 to 20% by mass.

[Monoepoxy compound (A2)]
Component (A2) is not particularly limited as long as it is an epoxy compound other than component (A1), but refers to a compound having one epoxy group in the molecule.
By using component (A2), it is possible to easily obtain a composition or a putty molded body that has appropriate flexibility and has excellent adhesion to the object to be coated.
Component (A2) may be used alone or in combination of two or more.

Component (A2) is preferably a monoglycidyl ether, specific examples of which include alkyl glycidyl ethers, phenyl glycidyl ethers (alkylphenyl glycidyl ethers, etc.), and among these, alkyl glycidyl ethers are preferred.
The alkyl moiety of the alkyl glycidyl ether and alkylphenyl glycidyl ether usually has 1 to 20 carbon atoms, preferably 5 to 18 carbon atoms, and more preferably 10 to 16 carbon atoms.

As component (A2), a compound synthesized by a conventionally known method may be used, or a commercially available product may be used.
Examples of the commercially available product include EPODIL 759 (alkyl (C12-13) glycidyl ether, manufactured by Evonik Corporation, epoxy equivalent: 275 to 290, viscosity: ≦8 mPa·s/25°C).

The epoxy equivalent of component (A2) is usually 50 to 1,000, preferably 100 to 600, more preferably 150 to 500.
When the epoxy equivalent of component (A2) is within the above range, a composition having excellent flexibility, adhesion to the coated object, etc. can be easily obtained.

When the present composition contains component (A2), it is possible to easily obtain a composition or a putty molded body having appropriate flexibility and excellent adhesion to the object to be coated. The content of component (A2) based on 100% by mass of the nonvolatile content of the composition is preferably 1 to 30% by mass, more preferably 2 to 15% by mass.

[Epoxy compound (A3)]
Component (A3) is not particularly limited as long as it is an epoxy compound other than components (A1) and (A2), but the resulting composition or putty molded product has heat resistance, high elastic modulus, dimensional stability, and chemical resistance. Epoxy resins are preferred because they can impart excellent mechanical and chemical properties such as.
Component (A3) may be used alone or in combination of two or more.

Examples of component (A3) include polymers or oligomers containing two or more epoxy groups in the molecule, and polymers or oligomers produced by a ring-opening reaction of the epoxy groups.

Such component (A3) includes, for example, bisphenol-type epoxy resin, glycidyl ester-type epoxy resin, glycidylamine-type epoxy resin, novolak-type epoxy resin, cresol-type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, Examples include epoxidized oil-based epoxy resins.

Among these, bisphenol-type epoxy resins are preferred because they can easily produce compositions and putty molded articles having appropriate hardness, elastic modulus, and heat resistance, and bisphenol A-type or bisphenol F-type epoxy resins are preferable. is more preferred, and bisphenol A type epoxy resin is particularly preferred.

Examples of such epoxy resins include epichlorohydrin-bisphenol A epoxy resin (bisphenol A diglycidyl ether type); epichlorohydrin-bisphenol AD epoxy resin; epichlorohydrin-bisphenol F epoxy resin; epoxy novolak resin; Alicyclic epoxy resin obtained from 3',4'-epoxyphenylcarboxymethane, etc.; brominated epoxy in which at least one of the hydrogen atoms bonded to the benzene ring in the epichlorohydrin-bisphenol A epoxy resin is substituted with a bromine atom Resin; aliphatic epoxy resin obtained from epichlorohydrin and aliphatic dihydric alcohol; polyfunctional epoxy resin obtained from epichlorohydrin and tri(hydroxyphenyl)methane.

Examples of the bisphenol A type epoxy resin include bisphenol A diglycidyl ether, bisphenol A (poly)propylene oxide diglycidyl ether, bisphenol A (poly)ethylene oxide diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol A. Examples include condensation products such as bisphenol A type diglycidyl ether such as (poly)propylene oxide diglycidyl ether.

As component (A3), a compound synthesized by a conventionally known method may be used, or a commercially available product may be used.
Component (A3) is preferably a compound that is liquid at room temperature (temperature of 15 to 25° C., hereinafter the same) from the viewpoint that a putty composition can be easily prepared.
Commercially available compounds that are liquid at room temperature include, for example, NPEL-128 (bisphenol A diglycidyl ether, manufactured by Nan Ya Plastics Corporation, epoxy equivalent: 180 to 190, viscosity: 12,000 to 15,000 mPa·s/25 °C), jER 825 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 170-180, viscosity: 4,000-7,000 mPa・s/25 °C), jER 828 (bisphenol A diglycidyl ether, Mitsubishi Chemical Corporation) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: 180-190, viscosity: 12,000-15,000 mPa・s/25°C), Epototh YD-128 (bisphenol A diglycidyl ether, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: 184-194) , viscosity: 11,000 to 15,000 mPa・s/25°C), Epotote YDF-170 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: 160 to 180, viscosity: 2,000 to 5,000 mPa・s/25 ), Epiclon 840 (manufactured by DIC Corporation, epoxy equivalent: 180-190, viscosity: 9,000-11,000 mPa・s/25°C), Epiclon 850 (manufactured by DIC Corporation, epoxy equivalent: 183-193) , viscosity: 11,000-15,000 mPa・s/25°C), Sumiepoxy ELA128 (manufactured by Sumitomo Chemical Co., Ltd.), DER331 (manufactured by DOW Chemical Co., Ltd., epoxy equivalent: 182-192, viscosity: 11,000-14, 000 mPa·s/25°C), and FLEP 60 (manufactured by Toray Fine Chemicals, epoxy equivalent: about 280, viscosity: about 17,000 mPa·s/25°C).

The epoxy equivalent of component (A3) is preferably 100 to 1,000, more preferably 150 to 600.
When the epoxy equivalent of component (A3) is within the above range, a composition with excellent quick drying properties can be easily obtained.

The viscosity of component (A3) is preferably 100 to 100,000 mPa·s/25°C, more preferably 500 to 50,000 mPa·s/25°C.
When the viscosity of component (A3) is within the above range, a composition with better sag resistance can be easily obtained.
The viscosity can be measured using a B-type viscometer (Visco Tester "VT6plus", manufactured by Thermo Scientific).

When the present composition contains component (A3), it is possible to easily obtain a composition or a putty molded body having excellent quick-drying properties, flexibility, and adhesion to the object to be coated. The content of component (A3) based on 100% by mass of nonvolatile matter is preferably 10 to 30% by mass, more preferably 15 to 25% by mass.

<Aliphatic amine (B)>
Component (B) is not particularly limited as long as it is an aliphatic amine, excluding the tertiary amines (amine compounds having only tertiary amino groups) described below.
By using component (B) together with component (C) and the like, a highly viscous, grease-like mixture can be easily obtained, and a composition with excellent sharpness and sag resistance can be easily obtained.
Component (B) may be used alone or in combination of two or more.

Amine compounds are distinguished by the type of carbon to which an amino group is bonded, and an aliphatic amine refers to a compound having at least one amino group bonded to an aliphatic carbon. Moreover, when component (B) is the following modified compound, the modified compound has at least one amino group bonded to an aliphatic carbon.
In addition, the aliphatic amine in the present invention refers to a compound other than an amine having a polyoxyalkylene structure (-(RO) _n -[R is an alkyl group, and n is a real number of 3 or more]). . Even when amines having such a polyoxyalkylene structure are used together with component (C) etc., it is difficult to obtain a highly viscous mixture like grease.

Examples of component (B) include alkylene polyamines, polyalkylene polyamines, alkylaminoalkylamines, and alicyclic amines.
Component (B) is preferably an amine compound other than an alicyclic amine, since it is a low-viscosity compound and a putty composition with excellent curability can be easily obtained, and alkylene polyamines, alkylene polyamines, More preferred are polyalkylene polyamines and alkylaminoalkylamines.
When an alicyclic amine is used, the resulting composition may have poor curability and drying properties.

Examples of the alkylene polyamine include a compound represented by the formula: "H ₂ NR ¹ --NH ₂ " (R ¹ is a divalent hydrocarbon group having 1 to 12 carbon atoms). , specifically methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 2,5- Examples include dimethyl-2,5-hexanediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and trimethylhexamethylenediamine.

The polyalkylene polyamine has, for example, the formula: "H ₂ N-(C _m H _2m NH) _n H" (m is an integer of 1 to 10. n is an integer of 2 to 10, preferably 2 ), specifically, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, Examples include nonaethylenedecamine, bis(hexamethylene)triamine, triethylene-bis(trimethylene)hexamine, and 4-aminomethyloctamethylenediamine.

The alkylaminoalkylamine may have, for example, the formula: "R ² ₂ N-(CH ₂ ) _p -NH ₂ " (R ² is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (provided that , at least one R ² is an alkyl group having 1 to 8 carbon atoms), p is an integer of 1 to 6), and specifically, dimethylaminoethylamine, diethylamino Examples include ethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminobutylamine, and the like.

Other aliphatic amines include tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, 3,3'-methyliminobis (propylamine), tris(2-aminoethyl)amine, bis(cyanoethyl)diethylenetriamine, bis(3-aminopropyl)ether, 1,2-bis(3-aminopropyloxy)ethane, octylamine, laurylamine, myristyl Amine, stearylamine, cocoalkylamine, bis(aminomethyl)cyclohexane, isophoronediamine, menzendiamine (MDA), N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8, 10-tetraoxaspiro[5,5]undecane, o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, 1,4 -bis(3-aminopropyl)piperazine, 1-(2'-aminoethylpiperazine), 1-[2'-(2''-aminoethylamino)ethyl]piperazine, and the like.

Specifically, the alicyclic amines include cyclohexanediamine, diaminodicyclohexylmethane (especially 4,4'-methylenebiscyclohexylamine), bis(4-amino-3-methylcyclohexyl)methane, 4,4' -isopropylidenebiscyclohexylamine, norbornanediamine, 2,4-di(4-aminocyclohexylmethyl)aniline, and the like.

Component (B) may further include modified products of the aforementioned compounds, such as fatty acid modified products such as polyamide amines, amine adducts with epoxy compounds, Mannich modified products, Michael adducts, ketimines, and aldimines.

Component (B) may be synthesized by a conventionally known method, or may be a commercially available product.
Examples of such commercial products include "JOINTMINE CT-4150" (manufactured by YUN THE INDUSTRIAL CO., LTD.) which is a modified aliphatic polyamine, "Amicure PACM" (manufactured by Evonik Corporation) which is an alicyclic polyamine, and aliphatic amine "AD-71" (manufactured by Ohtake Meishin Kagaku Co., Ltd.) is an epoxy adduct.

The molecular weight of component (B) is preferably 1,000 or less, more preferably 50 to 800, because it reacts quickly with component (A) and can easily obtain a composition with excellent room temperature curability. It is.

The active hydrogen equivalent of component (B) is preferably 10 to 1,000, more preferably 20 to 400, from the viewpoint of easily obtaining a composition and a putty molded body with excellent strength and drying properties. .

Component (B) preferably has a reaction ratio calculated by the following formula (1) from the viewpoint of easily obtaining a composition and a putty molded article having excellent sagging resistance and adhesion to the substrate. is preferably used in an amount of 0.7 to 1.2, more preferably 0.8 to 1.1.

Reaction ratio = {(Blend amount of component (B)/Active hydrogen equivalent of component (B)) + (Blend amount of component that is reactive to component (A)/Blend amount of component that is reactive to component (A) (Functional group equivalent of the component having)}/{(Amount of component (A) blended/Epoxy equivalent of component (A))+(Blend amount of component (B) reactive to component (B)) Functional group equivalent of component having reactivity with)} ...(1)

Here, the "component having reactivity with component (B)" in the above formula (1) includes, for example, components (D) and (E) which will be described later, and "component (A) with reactivity". Examples of the "component having reactivity with respect to the composition" include components (D), (E), and curing agents other than component (B), which will be described later. The "functional group equivalent" of each component means the mass (g) per 1 mol of functional groups obtained by dividing the number of mol of functional groups contained therein from the mass of 1 mol of these components.
As components (D) and (E) described below, compounds having an amino group or an epoxy group as a reactive group can be used, so depending on the type of reactive group, the reactivity with component (A) may be It is necessary to determine whether the component (B) has reactivity or has reactivity with component (B), and calculate the reaction ratio.

<Silica (C)>
Examples of component (C) include fumed silica, wet silica, and colloidal silica. Among these, fumed silica is preferred because a composition with better sag resistance can be easily obtained.
Note that component (C) does not include glass.
Component (C) may be used alone or in combination of two or more.

The fumed silica is a compound containing silicon oxide as a main component, and can be synthesized by a conventionally known method.
The fumed silica may be hydrophobic fumed silica in which at least a portion of the silanol groups on its surface are modified with an organic group, etc., but it is possible to easily obtain a composition with better sharpness and sagging resistance. Hydrophilic fumed silica is preferable from the viewpoint of high performance. In particular, it has been found that when hydrophilic fumed silica is mixed with component (B), a grease-like, highly viscous mixture can be easily obtained. Therefore, it is preferable to use hydrophilic fumed silica as component (C) because it is possible to thicken the present composition and to easily obtain a composition that has better sharpness and sag resistance. .

The specific surface area of the fumed silica measured by the BET method is preferably 30 to 450 m/g, more preferably 100 to 300 m/g, from the viewpoint of easily obtaining a composition with better sagging resistance. be.

The primary average particle diameter of component (C) is preferably 3 to 100 nm, more preferably 5 to 50 nm, from the standpoint of easily obtaining a composition with excellent sharpness and sagging resistance.
This primary average particle diameter can be observed, for example, with an electron microscope (50,000 to 200,000 times) and measured using an image analysis device.

As component (C), a commercially available product may be used.
Examples of commercial products of hydrophilic fumed silica include AEROSIL 90, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 255, AEROSIL 300, AEROSIL 380, AEROSIL OX 50, and AE. ROSIL TT 600, AEROSIL 200F, Examples include AEROSIL 380F, AEROSIL 200 Pharma, and AEROSIL 300 Pharma (all manufactured by Nippon Aerosil Co., Ltd.).

The content of component (C) based on 100% by mass of the nonvolatile content of the present composition is 5% by mass or more, preferably 5 to 40% by mass, more preferably 5.5 to 30% by mass.
When the content of component (C) is within the above range, a composition with better sharpness and sagging resistance can be easily obtained, and a putty molded body having appropriate flexibility can be formed. If the content of component (C) is less than 5% by mass, a composition with excellent sharpness and sagging resistance cannot be obtained. When the content of component (C) exceeds the upper limit of the above range, stirring and handling of the resulting composition may become difficult.

Further, when component (C) is hydrophilic fumed silica, the content of the hydrophilic fumed silica relative to 100% by mass of the nonvolatile content of the present composition is preferably 5 to 12% for the same reason as above. % by weight, more preferably 5.5-10% by weight.

<Acrylonitrile butadiene copolymer (D)>
This composition has excellent elongation, elasticity, and sag resistance, and can easily form a putty molded product with appropriate flexibility, and can increase the viscosity of the resulting composition. It is preferable to contain a copolymer (D).
Component (D) may be used alone or in combination of two or more.

Component (D) is not particularly limited as long as it is a copolymer obtained using acrylonitrile and butadiene; A copolymer having a structural unit content of 15 to 50% by mass is preferred.

Component (D) is preferably an acrylonitrile butadiene copolymer having a reactive group, having an acrylonitrile polybutadiene skeleton in the main chain, and an epoxy group or a functional group that reacts with an epoxy group (e.g., an amino group) at the end. , carboxy group, hydroxy group) is more preferable.
By using an acrylonitrile butadiene copolymer having a reactive group, it is possible to impart flexibility and improve elasticity without reducing the water resistance of the resulting putty molded product, and it is also possible to improve the elasticity of the putty molded product under pressure. Even in such cases, it is possible to easily obtain a putty molded body that can follow the pressure.

In addition, when this composition is a two-component type composition consisting of a main ingredient component and a curing agent component, and when component (D) is a copolymer having an epoxy group, the copolymer: It is preferably blended into the main ingredient component, and when component (D) is a copolymer having a functional group that reacts with an epoxy group, the copolymer is preferably blended into the curing agent component.

The viscosity of component (D) at 25° C. is preferably 50 to 400 Pa·s, from the viewpoint of being able to easily form a putty molded body having excellent elongation, elasticity, and sag resistance and having appropriate flexibility. More preferably, it is 100 to 300 Pa·s.

Component (D) may be synthesized by a conventionally known method, or may be a commercially available product.
Examples of commercial products of acrylonitrile butadiene copolymers having reactive groups include "Hypro 1300x16 ATBN" and "Hypro 1300x42 ATBN" having amino groups at the ends, and "Hypro 1300x42 ATBN" having carboxy groups at the ends. Examples include "Hypro 1300x8 CTBN", "Hypro 1300x31 CTBN", and "Hypox RA840" having an epoxy group at the end (all manufactured by CVC Thermoset Specialties).

When the present composition contains component (D), the content of component (D) based on 100 mass% of nonvolatile content of the present composition is preferably 10 mass% or more, more preferably 15 mass% or more, and preferably is 40% by mass or less.
When the content of component (D) is within the above range, it is possible to easily obtain a putty molded product having excellent elongation and elasticity and appropriate flexibility, and also has good sharpness, sagging resistance, and agitation properties. A composition with better properties and handling properties can be easily obtained. On the other hand, if the content of component (D) exceeds the above upper limit, the workability and sharpness of the resulting composition may deteriorate. Moreover, when the content of component (D) is less than the above-mentioned lower limit, the yield point elongation of the resulting putty molded body may decrease.

<Silane coupling agent (E)>
The present composition preferably contains a silane coupling agent (E) from the viewpoint of improving adhesion to the object to be coated.
Component (E) may be used alone or in combination of two or more.

Component (E) is not particularly limited, and conventionally known compounds can be used, but it must be a compound that has at least two functional groups in the same molecule and can contribute to improving the adhesion to the object to be coated. is preferable, for example, the formula: "X-SiMe _n Y _3-n " [n is 0 or 1, , a halogen group, a group in which a portion of a hydrocarbon group is substituted with one of these groups, or a group in which a portion of a hydrocarbon group is substituted with an ether bond, etc.) , Me is a methyl group, and Y is a hydrolyzable group (eg, an alkoxy group such as a methoxy group or an ethoxy group). ] is more preferable.

Component (E) is preferably a compound having an epoxy group or an amino group as a reactive group, more preferably a compound having an epoxy group. Specifically, "KBM-403" (γ-glycidoxypropyltrimethoxy Examples include silane (manufactured by Shin-Etsu Chemical Co., Ltd.) and "Sila Ace S-510" (manufactured by JNC Co., Ltd.).

When the present composition contains component (E), it is possible to easily obtain a composition or a molded article with excellent adhesion to the object to be coated. The content of E) is preferably 0.2 to 3% by weight, more preferably 0.5 to 2% by weight.

<Pigment (F)>
The present composition preferably contains a pigment (F) other than the silica (C).
Component (F) is not particularly limited, and conventionally known pigments can be used, and specific examples thereof include extender pigments, hollow pigments, colored pigments, and antirust pigments.
Component (F) may be used alone or in combination of two or more.

The extender pigments are not particularly limited, but include, for example, zinc oxide, talc, mica, clay, bentonite, potassium feldspar, wollastonite, glass flakes, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, and magnesium carbonate. , barium sulfate (e.g. barite powder), and gypsum. Among these, talc , mica , clay, calcium carbonate, kaolin, barium sulfate, potassium feldspar, and gypsum are preferred.

The hollow pigment is not particularly limited, but examples thereof include perlite, fly ash, resin hollow balloons, and ceramic balloons.

The colored pigments are not particularly limited, but include, for example, inorganic pigments such as carbon black, titanium dioxide, Bengara, iron oxide, iron hydroxide, ultramarine, and organic pigments such as phthalocyanine blue and phthalocyanine green.

The rust-preventing pigment is not particularly limited, but includes, for example, zinc powder, zinc alloy powder, zinc phosphate compounds, calcium phosphate compounds, aluminum phosphate compounds, magnesium phosphate compounds, zinc phosphite compounds, and zinc phosphate compounds. Calcium phosphate compounds, aluminum phosphite compounds, strontium phosphite compounds, aluminum tripolyphosphate compounds, zinc tripolyphosphate compounds, zinc molybdate compounds, aluminum molybdate compounds, cyanamide zinc compounds, borates Examples include compounds, nitro compounds, and composite oxides.

When the present composition contains component (F), it is possible to easily obtain a composition and a putty molded body having excellent effects as described above, and therefore, the amount of component (F) based on 100% by mass of the non-volatile content of the present composition can be easily obtained. The content is preferably 5 to 40% by weight, more preferably 10 to 35% by weight.

The pigment volume concentration (PVC) in the present composition is preferably 5 to 30%, more preferably 10 to 20%, from the viewpoint that it is possible to easily obtain a composition and a putty molded body having excellent effects. be.

The PVC refers to the total volume concentration of all pigments including the silica (C), pigment (F), etc., and can be specifically determined from the following formula.
PVC [%] = Total volume of all pigments in this composition x 100/Volume of non-volatile matter in this composition

The volume of nonvolatile matter in the present composition can be calculated from the mass and true density of the nonvolatile matter of the present composition. The mass and true density of the nonvolatile components may be measured values or values calculated from the raw materials used.

The volume of the pigment can be calculated from the mass and true density of the pigment used. The mass and true density of the pigment may be measured values or values calculated from the raw materials used. The measured value can be calculated, for example, by separating the pigment from other components from the nonvolatile components of the composition and measuring the mass and true density of the separated pigment.

<Other ingredients>
In addition to the above-mentioned components (A) to (F), the present composition may optionally contain an organic solvent, a curing agent other than component (B), an anti-sagging/settling agent, a curing accelerator , a plasticizer , A leveling agent, an inorganic dehydrating agent, an ultraviolet stabilizer, an ultraviolet absorber, an anti-aging agent, a dispersant, an antifoaming agent, etc. may be contained within the range that does not impair the object of the present invention.
These other components include conventionally known components.
Each of the other components may be used alone or in combination of two or more.

[Curing agent other than component (B)]
Examples of curing agents other than the component (B) include polyoxyalkylene polyamines, aromatic amine curing agents, heterocyclic amine curing agents, modified products thereof, such as fatty acid modified products such as polyamidoamine, and epoxy compounds. Examples include amine adducts with, Mannich modified products (e.g., phenalkamine, phenalkamide), Michael adducts, ketimines, and aldimines.

The polyoxyalkylene polyamine has a polyoxyalkylene structure (-(RO) _n -[R is an alkyl group, preferably an alkyl group having 2 to 6 carbon atoms, and n is a real number of 3 or more, preferably is a real number from 3 to 70]), specific examples include diethylene glycol bis(3-aminopropyl) ether) and tetramethylene glycol bis(3-aminopropyl) ether.

Examples of the aromatic amine curing agent include aromatic polyamine compounds having two or more primary amino groups bonded to a benzene ring.
More specifically, examples of the aromatic amine curing agent include phenylene diamine, naphthalene diamine, diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'- Diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, diaminodiethyl phenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4 '-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, and the like.

Examples of the heterocyclic amine curing agent include 1,4-diazacycloheptane, 1,11-diazacycloeicosane, and 1,15-diazacyclooctacosane.

Examples of the fatty acid modified product include polyamide amine obtained by reacting a dimer acid with a polyamine compound.
Commercially available products of the fatty acid modified product include, for example, Ancamide 910 and PEBAX Resins (manufactured by ELF Atochem, North America, Inc.).

When the present composition contains a curing agent other than the component (B), the content of the curing agent is preferably an amount that satisfies the reaction ratio, but the nonvolatile content of the present composition is 100% by mass. The total content of component (B) and curing agents other than component (B) is preferably 5 to 40% by mass, more preferably 5 to 30% by mass.

[Anti-sag/anti-settling agent]
Although the present composition may contain an anti-sagging/settling agent, it has sufficient sagging resistance even without the anti-sagging/settling agent, so it contains an anti-sagging/settling agent. You don't have to.
The anti-sagging and anti-settling agents include organic clay waxes such as stearate salts of Al, Ca, and Zn, lecithin salts, and alkyl sulfonates, polyethylene waxes, amide waxes, hydrogenated castor oil waxes, and oxidized polyethylene waxes. Examples include wax.

[Curing accelerator]
The composition preferably contains a curing accelerator that can contribute to adjusting, particularly accelerating, the curing rate.
Examples of the curing accelerator include conventionally known curing accelerators, but tertiary amines and the like are preferred from the standpoint of obtaining a coating composition with better curing speed and low-temperature curability.

The tertiary amine is not particularly limited, but includes, for example, triethanolamine, dialkylaminoethanol, triethylenediamine [1,4-diazabicyclo(2,2,2)octane], and 2,4,6-tri(dimethylaminomethyl). ) Phenol (eg, product name "Versamine EH30" (manufactured by BASF Japan Ltd.), product name "Ancamine K-54" (manufactured by Evonik Japan Ltd.)).

When the present composition contains the curing accelerator, the content of the curing accelerator is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass based on 100% by mass of the nonvolatile content of the present composition. Mass%.

≪Putty molded body, method for producing putty molded body≫
The putty molded body according to one embodiment of the present invention is formed from the present composition, and the method for producing the putty molded body according to one embodiment of the present invention includes applying the present composition to a construction site, and then curing the putty molded body. and manufacturing a putty molded body.

This composition can be applied to the construction site where you want to form a putty molded body, but this composition can be used as a seal when pouring a resin filler into a predetermined space for installing or fixing equipment or parts. Since it is suitably used as a stopper, it is applied to such equipment and parts (also referred to as objects to be coated).
The material of the object to be coated is the material of equipment, parts, etc., and specific examples thereof include steel, nonferrous metals (zinc, aluminum, etc.), stainless steel, and the like.
Examples of the object to be coated include structures such as ships, land structures, and bridges, with ship structures being particularly preferred, and ship stern tubes and rudder head bearings being particularly preferred.

The method for applying the present composition is not particularly limited, but any conventionally known method for applying a high viscosity composition can be employed, and preferred methods include brushing and troweling.

The method for curing the present composition is not particularly limited, and the present composition may be cured by heating at about 5 to 60°C to shorten the curing time, but it is usually heated at room temperature in the atmosphere for 1 hour. The composition is cured by leaving it for about 14 days.

The putty molded body is suitably used as a sealing material when pouring a resin filler into a predetermined space, so if it can serve as such a sealing material, there are no particular restrictions on its shape or thickness. However, the thickness is usually 1 cm or more, preferably about 1.5 to 2 cm.
According to the present composition, even when such a thick film is formed, and even when such a thick film is formed on a ceiling surface, no sagging occurs. It is also preferable in that it can be used in any location without restriction.

As for the putty molded body, the molded body formed as described above may be used as it is, or if necessary, the putty molded body may be coated with a top coat.
As the top coat, a conventionally known paint can be used, and examples of the top coat coating include common paint coating methods such as spray coating, roller coating, and brush coating.

The yield point elongation of the putty molded body is preferably 5% or more, more preferably 15% or more, and preferably 20% or more from the viewpoint of being able to follow the expansion and contraction of the object to be coated.
The elongation at yield point is specifically measured by the method described in Examples.

The putty molded body preferably has a tensile strength of 0.5 MPa or more, more preferably 1 MPa or more, in order to become a molded body that can withstand external forces (e.g., pressing force by a filler). Yes, preferably 1.2 MPa or more.
The tensile strength is specifically measured by the method described in Examples.

EXAMPLES Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

[Example 1]
Fatty acid modified epoxy 13.9 parts by mass, monoepoxy 6.9 parts by mass, epoxy resin 50 parts by mass, silica 5.6 parts by mass, calcium carbonate 20.8 parts by mass, silane coupling agent 1.4 parts by mass, and, A base ingredient was prepared by mixing 1.4 parts by mass of an antifoaming agent using a high-speed disperser.

In addition, 6.7 parts by mass of aliphatic amine 1, 30.3 parts by mass of polyamide amine, 30.3 parts by mass of NBR2, 5.7 parts by mass of silica, and 26.9 parts by mass of calcium carbonate were added using a high-speed disper. A curing agent component was prepared by mixing.

A composition was prepared by mixing 40.9 parts by mass of the obtained base component and 59.1 parts by mass of the curing agent component before coating.

[Examples 2 to 7 and Comparative Examples 1 to 9]
Same as Example 1 except that the raw materials and the blending amounts for the base resin component and curing agent component were changed as shown in Table 1, and the obtained base resin component and curing agent component were mixed at the mixing ratio shown in Table 1. A composition was prepared in the same manner.
In addition, the numerical values in the columns of the main component and curing agent component in Table 1 indicate parts by mass. Further, details of the raw materials in Table 1 are shown in Table 2.

<Applyability (cutting property)>
A groove of 50×150×15 mm in depth was created in a polyethylene plate. The compositions obtained in the Examples and Comparative Examples were applied using a spatula so that the grooves were completely filled. Specifically, the method of applying the composition is to apply the composition to the groove using a spatula and level it so that the thickness of the composition filling the groove is 15 mm and the surface is smooth. . The sharpness (separability) between the composition and the spatula was evaluated on a two-level scale when leveling the surface of the composition in this manner and when removing the spatula from the filled composition after leveling. When the spatula is removed from the filled composition, a smooth surface of the composition with good sharpness (no stringiness) is obtained. Cases in which the composition remained on the spatula side, stringiness occurred, and other cases where the composition and the spatula were not sharp and a smooth composition surface could not be obtained were marked as ×. Among these, ○ was considered to be a pass.

In addition, in order to evaluate the sharpness more objectively, the following tests were also conducted.
The compositions obtained in the Examples and Comparative Examples were applied to the grooves and smoothed in the same manner as in the above-mentioned coating properties (cutting properties).
Thereafter, the polyethylene plate coated with the composition is placed on a horizontal table, and a metal rod is inserted into the center of the groove from above perpendicularly to the surface to which the composition is applied until the tip of the metal rod contacts the bottom of the groove. A metal rod was inserted, and then, when the metal rod was pulled up in the vertical direction at a speed of 5 mm/s, the length at which the composition was removed from the metal rod was confirmed.
An example of a diagram in the case of ○ in the coating property (cutting property) is shown in FIG. 1, and an example of a diagram in the case of x in the coating property (cutting property) is shown in FIG. 2. Note that FIG. 1 specifically shows the results using the composition of Example 4, and FIG. 2 specifically shows the results using the composition of Comparative Example 8.

<Sagging resistance (vertical slump test)>
Using the compositions obtained in the Examples and Comparative Examples, a longitudinal slump test was conducted in accordance with JIS A 1439:2016, except that the test temperature was 23°C. Note that each composition was tested three times. The results were evaluated in three stages according to the following evaluation criteria. The results are shown in Table 1. The following cases of ○ or △ were considered to have passed.
・Evaluation criteria ○: No movement of the composition △: The composition moved, but the movement distance (distance from the bottom end of the groove part to the hanging tip) was less than 50 mm ×: The composition moved more than 50 mm

<Ease of mixing>
The base resin component and curing agent component obtained in the Examples and Comparative Examples were weighed out onto a polyethylene plate at the mass ratios (mixing ratios) shown in Table 1, and mixed uniformly with a spatula or trowel. The ease of mixing during this mixing was evaluated in three stages according to the following evaluation criteria. Cases marked with ○ below were considered to have passed.
・Evaluation criteria ○: The base resin component and the hardener component can be easily mixed. △: It is difficult to mix the base resin component and the hardener component. ×: The base resin component and the hardener component cannot be mixed uniformly.

<Elongation>
The compositions obtained in the Examples and Comparative Examples were applied onto a polyethylene plate using a spatula so that the resulting coating film had a thickness of 3 mm, and was cured at 23° C. for one day. Using the paint film peeled off from the polyethylene plate after curing, three test pieces (dumbbell-shaped test pieces using Type I) were prepared for each composition based on ASTM D 638, and tested using a tensile tester. (AGS-X, manufactured by Shimadzu Corporation) was used to measure the elongation at yield point (test speed 5 mm/min, test temperature 23° C.), and the average value of the elongation at yield point of each test piece was calculated. The results are shown in Table 1.
In addition, as an accelerated test, the average value of the elongation at yield point of the test pieces was calculated in the same manner except that the curing conditions were changed to 60° C. for 7 days. The results are shown in Table 1.

Specifically, the elongation at yield point was calculated from the following formula based on the elongation at break of the test piece, and the average value of three test pieces was used for evaluation. The results are shown in Table 1.
Elongation rate (%) = 100 x (LL ₀ )/L ₀
L ₀ : Length of test piece before test, L: Length of test piece at breakage

<Tensile strength>
The compositions obtained in the Examples and Comparative Examples were applied onto a polyethylene plate using a spatula so that the resulting coating film had a thickness of 3 mm, and was cured at 23° C. for one day. Using the paint film peeled off from the polyethylene plate after curing, three test pieces (dumbbell-shaped test pieces using Type I) were prepared for each composition based on ASTM D 638, and tested using a tensile tester. (AGS-X, manufactured by Shimadzu Corporation), the tensile strength was measured (test speed: 5 mm/min, test temperature: 23°C), and the average value of the tensile strength of each test piece was calculated. . The results are shown in Table 1.
In addition, as an accelerated test, the average value of the tensile strength of the test pieces was calculated in the same manner except that the curing conditions were changed to 60° C. for 7 days. The results are shown in Table 1.

The tensile strength refers to the maximum strength when a test piece breaks, and was calculated from the following formula, and the average value of three test pieces was used for evaluation. The results are shown in Table 1.
Tensile strength (MPa) = F/Wt
F: Force at break, W: Width (mm) of parallel portion of punching blade shape, t = Thickness of parallel portion of punching blade shape

Claims (6)

A putty composition containing an epoxy compound (A), an aliphatic amine (B) and a silica (C),
The content of the silica (C) is 5% by mass or more based on 100% by mass of nonvolatile content of the putty composition,
The silica (C) is hydrophilic fumed silica,
The epoxy compound (A) includes a fatty acid-modified epoxy compound (A1),
Putty composition. The putty composition according to claim 1 , further comprising an acrylonitrile butadiene copolymer (D). The putty composition according to claim 2 , wherein the content of the copolymer (D) is 10 to 40% by mass based on 100% by mass of nonvolatile content of the putty composition. The putty composition according to any one of claims 1 to 3 , which is used for ships. A putty molded body formed from the putty composition according to any one of claims 1 to 4 . A method for producing a putty molded body, comprising the step of applying the putty composition according to any one of claims 1 to 4 to a construction site and then curing the putty composition to produce a putty molded body.